JPH11130723A - Dicyclohexyl-2,3,3 ', 4'-tetracarboxylic acid compound or dianhydride thereof and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a novel dicyclohexyltetracarboxylic acid compound or a dianhydride thereof and a method for producing the same. SOLUTION: Cyclohexyl-2,3,3 ', 4'-
Cyclohexyl-2,3,3 ′, comprising a step of hydrogenating a tetracarboxylic acid compound, its dianhydride and biphenyl-2,3,3 ′, 4′-tetracarboxylic acid ester.
The present invention relates to a method for producing a 4′-tetracarboxylic acid compound or a dianhydride thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dicyclohexyltetracarboxylic acid compound, dicyclohexyl-2,3,3 ', 4'-tetracarboxylic acid, ester or dianhydride thereof, and a method for producing the same. .

[0002]

2. Description of the Related Art Conventionally, dicyclohexyltetracarboxylic acid obtained by hydrogenating an aromatic tetracarboxylic acid industrially produced or dianhydride thereof is disclosed in
Dicyclohexyl- described in JP-A-96147.
Only 3,3 ', 4,4'-tetracarboxylic acid or its dianhydride is known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel dicyclohexyltetracarboxylic acid or a dianhydride thereof and a method for producing the same.

[0004]

That is, the present invention provides:
Dicyclohexyl-2,3 represented by the following general formula
It relates to a 3 ', 4'-tetracarboxylic acid compound.

Embedded image (In the formula, X represents a hydrogen atom or an alkyl group having 1 or more carbon atoms.) Further, the present invention provides dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid represented by the following general formula: Related to anhydride.

Embedded image Further, the present invention relates to biphenyl-2,3,3 ', 4'
Dicyclohexyl-2,2 comprising a step of hydrogenating the tetracarboxylic acid ester with a hydrogenation catalyst such as a noble metal hydrogenation catalyst or a noble metal supported catalyst, and further comprising a step of hydrolyzing and dehydrating if necessary. ,
The present invention relates to a method for producing a 3 ′, 4′-tetracarboxylic acid compound or a dianhydride thereof.

[0005] The dicyclohexyl-2,3,
Examples of the 3 ′, 4′-tetracarboxylic acid compound include dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid,
Dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid methyl ester, dicyclohexyl-2,3,3
3 ′, 4′-tetracarboxylic acid ethyl ester, dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid isopropyl ester, dicyclohexyl-2,3
3 ', 4'-tetracarboxylic acid n-butyl ester and the like can be mentioned.

The biphenyl used in the present invention
2,3,3 ', 4'-tetracarboxylic acid alkyl ester is a known compound, for example, JP-B-60-333.
No. 79 and Japanese Patent Publication No. 61-57821. For example, a phthalic acid diester is subjected to a coupling reaction in the presence of oxygen using a catalyst of oxygen, a palladium salt and 1,10-phenanthroline or bipyridyl, and then formed biphenyl-
After removing the catalyst and the solvent from a mixture containing an alkyl ester such as 2,3,3 ′, 4′-tetracarboxylic acid methyl ester, the mixture can be obtained by a distillation method.
This biphenyl-2,3,3 ′, 4′-tetracarboxylic acid methyl ester has a boiling point of 200 (1 mmHg) ° C.
It is a white crystal with a melting point of 75 ° C.

The dicyclohexyl-2,3 of the present invention
The 3 ′, 4′-tetracarboxylic acid compound can be preferably produced as follows. That is, the above-mentioned biphenyl-2,3,3 ', 4'-tetracarboxylic acid ester is dissolved in a solvent, and a hydrogenation reaction is performed in the presence of a hydrogenation catalyst. As a solvent to be used, biphenyl-2,
Dissolving 3,3 ′, 4′-tetracarboxylic acid ester,
Any solvent that does not cause a side reaction at the time of the hydrogenation reaction may be used, and aliphatic alcohols having 1 or more carbon atoms such as methyl alcohol and ethyl alcohol, and esters having 3 or more carbon atoms such as methyl acetate and ethyl acetate. , Tetrahydrofuran, dimethyl ether, diisopropyl ether and the like having 4 carbon atoms
The above-mentioned ethers, hydrocarbons having 6 or more carbon atoms such as normal hexane and cyclohexane are exemplified. Examples of the hydrogenation catalyst include a metal rhodium powder, a metal ruthenium powder, and a catalyst in which these metals are supported on a carrier such as activated carbon, alumina, diatomaceous earth, and silica. In the case of a supported catalyst, 0.1-10% by weight in terms of noble metal
Is preferably carried. The amount of the hydrogenation catalyst used is usually 2 to 50% by weight in terms of metal based on biphenyl-2,3,3 ', 4'-tetracarboxylic acid ester.
It is preferred that

The conditions under which the above-mentioned hydrogenation reaction is carried out vary depending on the catalyst, but usually the hydrogen pressure is several kg / cm ² -1.
It is preferably 00 kg / cm ² , especially 20-50 kg / cm ² , the temperature is 20-200 ° C., particularly 50-150 ° C., and the reaction time is preferably several tens of minutes to 24 hours. Regarding the progress and termination of the hydrogenation reaction,
The determination can be made by obtaining the amount of consumed hydrogen from the pressure gauge. After completion of the reaction, the catalyst was removed from the reaction mixture by a filtration operation, the solvent was removed by reducing the pressure of the system, and dicyclohexyl-2,3,3 ′, distilled at a pressure of 1 to 20 mmHg and a temperature of 200 to 250 ° C. 4'-tetracarboxylic acid ester can be obtained.

[0009] The dicyclohexyl-2,3,
3 ′, 4′-Tetracarboxylic acid can be obtained by hydrolyzing the above-mentioned dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid ester. The hydrolysis can be carried out by heating, acid or alkali hydrolysis in water followed by acid precipitation. The acid or alkali may be a catalytic amount. As the conditions for the hydrolysis reaction, the temperature is usually 2
0-250 ° C., pressure 1-40 kg / cm ² , amount of water is dicyclohexyl-2,3,3 ′, 4′-
It is preferably several times to 100 times the weight of the tetracarboxylic acid ester, and the reaction time is preferably several tens minutes to 24 hours.

[0010] The dicyclohexyl-2,3 of the present invention
3 ′, 4′-Tetracarboxylic dianhydride can be obtained by dehydrating and diclosing dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid to obtain an anhydride. The dehydration can be performed by a method of heating under normal pressure and reduced pressure while flowing an inert gas, or a method of heating and dissolving in acetic anhydride for crystallization. As the conditions for the above-mentioned heat dehydration, the pressure is 1-750 mmHg and the temperature is 150-
It is preferable that the temperature is 250 ° C. and the time is about several minutes to 24 hours. Dicyclohexyl-2,3,3 ', 4'-
The tetracarboxylic dianhydride can be obtained by sublimating impurities simultaneously with the dehydration reaction. In addition, the dehydration with acetic anhydride is performed when the amount of acetic anhydride is dicyclohexyl-
The amount is about 10 times the molar amount of 2,3,3 ', 4'-tetracarboxylic acid, the time is about 1-3 hours, the solvent and acetic anhydride are removed under reduced pressure, and the mixture is left to cool. Dicyclohexyl-2,3,3 ', 4'-tetracarboxylic dianhydride can be obtained.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. Example 1 Preparation of dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid methyl ester Biphenyl-2,3,3 ′ having a melting point of 75 ° C. was placed in a 1-liter autoclave equipped with a stirrer. 4,4'-tetracarboxylic acid methyl ester [orthophthalic acid dimethyl ester is subjected to a coupling reaction by heating at normal pressure for 5 to 10 hours in the presence of oxygen using a catalyst of palladium acetate and 1,10-phenanthroline to form biphenyl-
From a mixture containing an alkyl ester such as 2,3,3 ', 4'-tetracarboxylic acid methyl ester, the catalyst is reduced and filtered, the solvent is removed under reduced pressure, and distillation and crystallization by methyl alcohol are carried out. 77.1)
g (0.2 mol), 386 g of tetrahydrofuran, and 7.7 g of a catalyst in which 5% by weight of rhodium is supported on activated carbon (manufactured by N-Chemcat), and hydrogen pressure of 30
The hydrogenation reaction was performed at a reaction temperature of 100 ° C./kg/cm ² until a predetermined amount of hydrogen was absorbed. After the reaction, the catalyst was removed by filtration, followed by heating to 50 ° C. by an evaporator to remove tetrahydrofuran as a solvent, and a white waxy methyl dicyclohexyl-2,3,3 ′, 4′-tetracarboxylate. 73.0 g (0.19 mol) of ester
I got FIG. 1 shows the infrared absorption spectrum of this white wax (measured by the KBr method using a JAS.CO FT / IR-5300 type infrared spectrophotometer manufactured by JASCO Corporation). ¹
As a result of analysis by 1 H-NMR (GSX-400 Nuclear Magnetic Resonance Spectrometer manufactured by JEOL Ltd.), benzene nuclear hydrogen and hydrogen bonded to a carbon-carbon double bond were not detected, and the hydrogenation reaction was completed. It was confirmed that.

Example 2 Production of dicyclohexyl-2,3,3 ', 4'-tetracarboxylic acid Dicyclohexyl-2,3,3', 4'- was added to a 1-liter autoclave equipped with a stirrer. 40 g (0.1 mol) of tetracarboxylic acid methyl ester and 800 g of water were charged, and the inside of the tank was inactivated with nitrogen. The mixture was heated to 200 ° C. and stirred for 8 hours to react. After the completion of the reaction, excess water was removed from the reaction solution by an evaporator, and the solution was dried.
3.2 g (0.097 mol) of dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid as white powdery crystals was obtained. FIG. 2 shows the infrared absorption spectrum of this crystal.
As a result of the analysis by ¹ H-NMR, the integrated intensity ratio of the absorption based on 9 ppm of the carboxyl group proton and the absorption based on 0.9 to 3.0 ppm of the cyclohexane ring proton is as follows.
4.3: 18.1, which was in agreement with the theoretical value. The melting point of the white crystal was 118.0-123.5 ° C.

Example 3 Preparation of dicyclohexyl-2,3,3 ', 4'-tetracarboxylic dianhydride Dicyclohexyl-2,3,3', 4'-tetracarboxylic acid was placed in a 1-liter glass container for sublimation. 13.7 g of acid
(0.04 mol), pressure 1 mmHg, temperature 20
The dehydration reaction was performed at 0 ° C. for 10 hours. After cooling, white crystals were obtained in which impurities were sublimated and removed simultaneously with the dehydration reaction. FIG. 3 shows the infrared absorption spectrum of this crystal. Also ¹
As a result of analysis by H-NMR, it was confirmed that there was no absorption based on 9 ppm of carboxyl group protons, and the product was an anhydride. The melting point of this crystal was 87.3-9.
0.8 ° C.

Comparative Example 1 Biphenyl-2,3,3 ', 4'-tetracarboxylic acid was added to 1 liter of autoclave used in Example 1.
1 g (0.2 mol), 386 g of tetrahydrofuran, and 6.6 g of a catalyst having 5% by weight of rhodium supported on activated carbon (manufactured by N-Chemcat Co.) were charged, and hydrogen pressure was 30 kg / cm ² and the reaction temperature was 100 ° C. Stirring was continued for 5 hours, but no absorption of hydrogen was recognized, and the hydrogenation reaction did not proceed, and dicyclohexyl-2,3,3 ', 4'-tetracarboxylic acid methyl ester could not be obtained.

Comparative Example 2 To 1 liter of autoclave used in Example 1 was added 58.8 g (0.2 mol) of biphenyl-2,3,3 ', 4'-tetracarboxylic dianhydride and tetrahydrofuran. 38
6 g, and 5.9 g of a catalyst having 5% by weight of rhodium supported on activated carbon (manufactured by N-Chemcat Co.) were charged.
Stirring was continued at a hydrogen pressure of 30 kg / cm ² and a reaction temperature of 100 ° C. for 5 hours, but no absorption of hydrogen was observed, the hydrogenation reaction did not proceed, and methyl dicyclohexyl-2,3,3 ′, 4′-tetracarboxylate was obtained. The ester could not be obtained.

[0016]

According to the present invention, a novel dicyclohexyl-2,2,2, which is a polymer raw material or a precursor thereof, is obtained.
A 3 ′, 4′-tetracarboxylic acid compound or a dianhydride thereof can be obtained.

Further, according to the present invention, a dicyclohexyl-2,2,3 ', 4'-tetracarboxylic acid compound or a dianhydride thereof can be easily produced.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of dicyclohexyl-2,2,3 ′, 4′-tetracarboxylic acid methyl ester obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of dicyclohexyl-2,2,3 ′, 4′-tetracarboxylic acid obtained in Example 2.

FIG. 3 is an infrared absorption spectrum of dicyclohexyl-2,2,3 ′, 4′-tetracarboxylic dianhydride obtained in Example 3.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 69/75 C07C 69/75 Z C07D 307/89 C07D 307/89 Z // C07B 61/00 300 C07B 61/00 300

Claims (3)

[Claims] 1. A dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic acid compound represented by the following general formula. Embedded image (In the formula, X represents a hydrogen atom or an alkyl group having 1 or more carbon atoms.) 2. A dicyclohexyl-2,3,3 ′, 4′-tetracarboxylic dianhydride represented by the following general formula. Embedded image 3. A step of hydrogenating biphenyl-2,3,3 ′, 4′-tetracarboxylic acid ester with a hydrogenation catalyst such as a noble metal hydrogenation catalyst or a noble metal supported catalyst, if necessary. The method for producing a dicyclohexyl-2,2,3 ', 4'-tetracarboxylic acid compound or a dianhydride thereof according to claim 1 or 2, further comprising a step of performing hydrolysis and dehydration treatment.